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Intramolecular hydroamination of alkynes catalysed by late transition metals

The cyclisation of 6-aminohex-1-yne to 2-methyl-1,2-dehydropiperidine in the presence of late transition metal catalysts was examined. The highest catalytic activity was observed for [Cu(CH3CN)4]PF6, as well as with Group 12 metal salts. Slightly lower conversions were obtained with the rhodium(I) and palladium(II) complexes [Rh(COD)(DiPAMP)]BF4 and [Pd(Triphos)][BF4]2. Catalysis was also observed with complexes of all group 9 to 12 metals and [Ru3(CO)12]. All catalytically active complexes contain a metal with a d8 or d10 electronic configuration. This observation allows preliminary conclusions about the mechanism to be made.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Palladium-catalyzed heteroaryl thioethers synthesis overcoming palladium dithiolate resting states inertness: Practical road to sulfones and NH-sulfoximines

We provide efficient synthetic access to heteroaryl sulfones in two-steps using a simple palladium?1,1?-bis[(diphenyl)phosphanyl]ferrocene catalyst to form in high yields variously functionalized heteroaromatic thioethers. Pyridinyl-containing substrates can be subsequently selectively oxidized into sulfones and NH-sulfoximines by using very mild oxidation conditions with a high functional group tolerance. In the palladium-catalyzed C?S coupling of heteroaromatic thiols, reactivity limitation is attached with electron-deficient thiols. We show that this limitation can be resolved by the successful use of 2-bromoheteroarenes in the C?S coupling. We established herein that this choice of heteroaryl electrophilic reagent in palladium-catalyzed C?S bond formation allows overcoming palladium dithiolate out-of-cycle resting state inertness. This was illustrated in the stoichiometric reactivity study of the palladium dithiolate formed from 4-trifluoromethylbenzen-1-thiol ?isolated and characterized by multinuclear NMR and XRD? with both 2-chloropyridine and 2-bromopyridine.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis of pincer ruthenium RuCl(CNN)(PP) catalysts from [RuCl(mu-Cl)(eta6-p-cymene)]2

The cationic [RuCl(eta6-p-cymene)(HCNNa)]Cl (1a) (HCNNa = 1-(6-arylpyridin-2-yl)methanamine) and the neutral RuCl 2(eta6-p-cymene)(HCNNb) (1b) (HCNN b = 2-aminomethylbenzo[h]quinoline) complexes have been obtained by reaction of the precursor [RuCl(mu-Cl)(eta6-p-cymene)] 2 with the corresponding nitrogen ligand (HCNNa and HCNNb) in THF. Complex 1a reacts cleanly with monodentate (P = PPh3) and bidentate phosphines (PP = dppb, dppf) in ethanol in the presence of NEt3, affording the pincer catalysts RuCl(CNN a)(PPh3)2 (2) and RuCl(CNNa)(PP) (PP = dppb 3, dppf 4). Similarly, the benzo[h]quinoline pincer derivative RuCl(CNNb)(dppb) (5) is obtained from 1b and dppb. Complex 3 has also been prepared in a one-pot reaction from [RuCl(mu-Cl)(eta6-p- cymene)]2, HCNNa, and dppb in ethanol. Similarly, the chiral complex RuCl(CNNa)((R,S)-Josiphos) was isolated as a single stereoisomer by treatment of [RuCl(mu-Cl)(eta6-p-cymene)] 2 with HCNNa and (R,S)-Josiphos in 1-butanol. Reaction of 1a and 1b with dppb affords cymene diphosphine species by displacement of the HCCN ligand.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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31P NMR Spectra of Chelated (Diphosphine)rhodium Complexes in Solution

The 31P<1H> FT NMR spectra of Rh complexes that form in solution via ligand exchange of diphosphines with HRh(CO)(PPh3)3 have been scanned in order to characterize the complexes that form since with certain diphosphines such solutions catalyze selective olefin hydroformilation.It is shown that these diphosphines readily form Rh complexes under NMR conditions that exhibit 16-line multiplet spectra.The multiplets were simulated with AB2X and ABCX (A, B, C = 31P, X = 103Rh) models and are attributed to approximately trigonal-bipyramid complexes of formula HRh(CO)(P<*>P)(PR3), )1.5>2, and HRh(CO)(P<*>P)(P<*>P))m, where R = PPh3 or PEtPh2, m = monodentate, and P<*>P = certain diphosphines including <(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)>bis(diphenylphosphine), diop, trans-1,2-bis-(diphenylphosphino)methyl)cyclobutane, t-bdcb, 1,1′-bis(diphenylphosphino)ferrocene, fdpp-1, and 1,1′-bis(bis(p-(trifluoromethyl)phenyl)phosphino)ferrocene, fdpp-2.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Various Coordination Modes of 1,1′-Bis(diphenylphosphino)ferrocene, dppfe, with Metals. Syntheses and X-Ray Structural Characterization of Metal Carbonyl Complexes of dppfe, MeCCo3(CO)7-dppfe and 2dppfe

Thermal reaction of MeCCo3(CO)9 with dppfe has afforded MeCCo3(CO)7-dppfe (2), where three terminal carbonyls shift to bridging positions and dppfe functions as a bridging ligand.Photochemical reaction of Mn2(CO)10 with dppfe followed by further photolysis with CCl4 has yielded 2dppfe (3).Two new types of coordination mode of dppfe as a bidentate ligand have been demonstrated by X-ray molecular analyses of 2 and 3 instead of a chelational type of coordination.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Phosphorus-chiral diphosphines as ligands in hydroformylation. An investigation on the influence of electronic effects in catalysis

The phosphorus-chiral diphosphine 1,1?-bis(1-naphthylphenylphosphino)ferrocene (1a) and its new electronically modified derivatives 1b-d bearing methoxy and/or trifluoromethyl groups in para positions of the phenyl rings were investigated as ligands in rhodium-catalyzed (asymmetric) hydroformylation. Depending on ligand basicity, high-pressure NMR and IR characterization of the respective (diphosphine) rhodium dicarbonyl hydride precursor complexes revealed subtle differences in the occupation of bis-equatorial (ee) and equatorialapical (ea) coordination geometries. The high ee:ea ratio of the four complexes contrasted with the clear ea preference observed for the related achiral compound dppf (1,1?-bis-(diphenylphosphino)ferrocene). In the hydroformylation of styrene the best result (50% ee) was obtained by employing the best pi-acceptor ligand 1c, incorporating two p-trifluoromethyl substituents. Substrate electronic variations using 4-methoxystyrene and 4-chlorostyrene showed a pronounced influence on turnover frequencies, branched/linear aldehyde product ratios, and enantiodiscrimation, whereas in the hydroformylation of 1-octene ligand electronic perturbations did affect only the rate, but not the selectivity of the reaction.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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New Mono-Dinitrogen Complexes of Molybdenum That Produce Ammonia and Hydrazine

A new, extensive series of mono-N2 complexes of molybdenum is reported.The sodium amalgam reduction of MoCl3(triphos), where triphos=PhP(CH2CH2PPh2)2, in tetrahydrofuran solution in the presence of 2L or L2 and with a deficiency of N2 led to the formation of Mo(N2)(triphos)(L2) (1A-F): 1A, L2=2 PPhMe2; 1B, L2=Me2PCH2PMe2; 1C, L2=1,2-(Me2As)2C6H4; 1D, L=Ph2PCH2PPh2; 1E, L2=Ph2PCH2CH2PPh2; 1F, L2=1,1′-(Ph2PC5H4)2Fe, DPPFe.Complexes 1C and 1E were each a mixture of isomeric mono-N2 complexes.Complex 1F was isolated together with Mo(triphos)(eta2-DPPFe)(eta1-DPPFe).Complexes 1A-F all reacted with HBr in CH2Cl2 to afford ammonia, hydrazine, and N2 (and some H2) in varying yields.The highest yield of ammonia was obtained from 1F, and the highest yield of hydrazine was obtained from 1A (HCl/toluene at 70 deg C).

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Copper(I) heteroleptic bis(NHC) and mixed NHC/phosphine complexes: Syntheses and catalytic activities in the one-pot sequential CuAAC reaction of aromatic amines

A series of 2-coordinate heteroleptic Cu(I) complexes of the general formula [Cu(IPr)(L)]PF6 (2-5, L = NHC or phosphine) have been synthesized via either (i) chlorido substitution by phosphine or in situ generated free NHC or (ii) the Ag-NHC transfer protocol using [CuCl(IPr)] (1) as a precursor (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene). The reactions of precursor 1 with diphosphine ligands afforded 3-coordinate heteroleptic Cu(I) complexes of the type [Cu(IPr)(L2)]PF6 (6 and 7, L2 = diphosphine). Complexes 1-7 have been subjected to a catalytic one-pot sequential CuAAC study, in which aromatic amines serve as the precursors to aryl azides. Hetero-bis(NHC) complexes 2-4 proved to be generally superior compared to their mixed NHC/phosphine counterparts 5-7. Overall, complex [Cu(Bn2-imy)(IPr)]PF6 (2), bearing the Bn 2-imy (Bn2-imy = 1,3-dibenzyl-imidazolin-2-ylidene) coligand, showed the best catalytic performance.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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FUSED MULTI-CYCLIC SULFONE COMPOUNDS AS INHIBITORS OF BETA-SECRETASE AND METHODS OF USE THEREOF

The present invention provides a new class of compounds useful for the modulation of beta-secretase enzyme (BACE) activity. The compounds have a general Formula I: wherein variables A5, A6, A8, R1, R2, R3, R7, X, Y, n and o of Formula I, independently, are defined herein. The invention also provides pharmaceutical compositions comprising the compounds, and corresponding uses of the compounds and compositions for treatment of disorders and/or conditions related to A-beta plaque formation and deposition, resulting from the biological activity of BACE. Such BACE mediated disorders include, for example, Alzheimer’s Disease, cognitive deficits, cognitive impairments, schizophrenia and other central nervous system conditions. The invention further provides compounds of Formula II and sub-formula embodiments thereof, compounds of Formula III, intermediates and processes and methods useful for the preparation of compounds of Formulas I-III, and sub-Formulas thereof.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis and structures of 1,1?-bis(diphenylphosphino)metallocenyl complexes M(eta 5-C5H4PPh2) 2Ru(H2O)2(OTs)2 (M = Fe, Ru, or Os)

The reaction of equimolar amounts of M(eta5-C 5H4PPh2)2 (M = Fe, Ru, or Os) and [Ru(H2O)6](OTs)2 afforded the M(eta5-C5H4PPh2) 2Ru(H2O)2(OTs)2 complexes, which were characterized by elemental analysis and 1H, 13C, and 31P NMR spectroscopy. The structure of the osmocene complex was established by X-ray diffraction.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate